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P. Ciuffreda et al. / Tetrahedron 56 (2000) 317–321
119.50, 118.47, 20.28; m/z (EI) 202 (Mϩ, 7), 160 (110), 131
(46), 114 (11), 103 (15), 77 (20).
1-Butyryloxy-5-hydroxynaphthalene (12). Column chro-
matography purification (light petroleum/ethyl acetate,
90:10, v/v) of the crude product affords compound 12
(65%) as a white solid, mp 112–113ЊC; (Found: C, 73.1;
H, 6.3. C14H14O3 requires C, 73.03; H, 6.13%); nmax (KBr)
3410, 1740, 1601 cmϪ1; dH (500 MHz, CDCl3) 7.98 (1 H, d,
J7.7 Hz, 2-H), 7.38 (1 H, dd, J7.7 and 7.7 Hz, 3-H), 7.33
(1 H, d, J7.7 Hz, 8-H), 7.21 (1 H, d, J7.7 Hz, 4-H), 7.18
(1 H, dd, J7.7 and 7.7 Hz, 7-H), 6.54 (1 H, d, J7.7 Hz,
6-H), 2.73 (2 H, t, J7.0 Hz, OCOCH2CH2CH3), 1.90 (2 H,
tq, J7.0 and 7.0 Hz, OCOCH2CH2CH3) 1.12 (3 H, t,
J7.0 Hz, OCOCH2CH2CH3); dC (125.76 MHz, CDCl3)
173.25, 152.67, 147.06, 128.69, 127.39, 126.70, 125.02,
120.97, 119.18, 113.73, 109.97, 37.03, 19.33, 14.45; m/z
(EI) 230 (Mϩ, 6), 160 (100), 131 (28), 115 (5), 103 (15),
77 (22).
1-Acetoxy-4-hydroxynaphthalene (7b). Yield: 89%, white
solid, mp 131–132ЊC (lit.10b mp 130–131.5ЊC); nmax (KBr)
3420, 1739, 1603 cmϪ1; dH (500 MHz, CDCl3) 8.15 (1 H,
dd, J7.7 and 1.4 Hz, 5-H), 7.64 (1 H, dd, J7.7 and
1.4 Hz, 8-H), 7.40 0(1 H, ddd, J7.7, 7.7 and 1.4 Hz,
7-H), 7.37 (1 H, ddd, J7.7, 7.7 and 1.4 Hz, 6-H), 6.93
(1 H, d, J8.4 Hz, 2-H), 6.68 (1 H, d, J8.4 Hz, 3-H),
2.41 (3H, s, OCOCH3); dC (125.76 MHz, CDCl3) 170.65,
150.99, 147.88, 138.97, 127.32, 126.60, 125.14, 122.53,
120.59, 117.92, 106.87, 20.64; m/z (EI) 202 (Mϩ, 8), 160
(100), 131 (36), 115 (4), 103 (18), 77 (32).
1-Acetoxy-5-hydroxynaphthalene (8a). Yield: 40%, white
solid, mp 149–150ЊC (lit.16 mp 156ЊC); nmax (KBr) 3439,
1728, 1602 cmϪ1; dH (500 MHz, CDCl3) 8.00 (1 H, d,
J7.7 Hz, 2-H), 7.39 (1 H, dd, J7.7 and 7.7 Hz, 3-H),
7.35 (1 H, d, J8.4 Hz, 8-H), 7.22 (1 H, d, J7.7 Hz,
4-H), 7.19 (1 H, dd, J8.4 and 8.4 Hz, 7-H), 6.56 (1 H, d,
J8.4 Hz, 6-H), 2.45 (3H, s, OCOCH3); dC (125.76 MHz,
CDCl3) 170.35, 150.98, 147.21, 128.05, 126.69, 125.84,
124.56, 120.04, 118.64, 113.43, 109.12, 21.00; m/z (EI)
202 (Mϩ, 10), 160 (100), 131 (35), 115 (6), 103 (25), 77
(27).
1-Acetoxy-3-hydroxynaphthalene (15). Yield: 80%,
viscous oil. nmax (thin film) 3395, 1736, 1603 cmϪ1; dH
(500 MHz, CDCl3) 7.74 (1 H, d, J8.4 Hz, 8-H), 7.59
(1 H, d, J8.4 Hz, 5-H), 7.40 (1 H, dd, J8.4 and 8.4 Hz,
6-H), 7.32 (1 H, dd, J8.4 and 8.4 Hz, 7-H), 6.95 (1 H,
d, J2.8 Hz, 4-H), 6.90 (1 H, d, J2.8 Hz, 2-H), 2.44
(3H, s, OCOCH3); dC (125.76 MHz, CDCl3) 169.73,
153.05, 147.42, 135.15, 127.05, 126.58, 123.95,
122.64, 121.04, 110.73, 107.94, 21.0; m/z (EI) 202
(Mϩ, 12), 160 (100), 131 (33), 115 (4), 103 (13), 77
(22).
6-Acetoxy-1-hydroxynaphthalene (8b). Yield: 54%,
viscous oil; (Found: C, 71.4; H, 4.8. C12H10O3 requires C,
71.28; H, 4.98%); nmax (thin film) 3437, 1734, 1602 cmϪ1
;
2-Acetoxy-6-hydroxynaphthalene (19a). Yield 93%,
white solid, mp 148–149ЊC (lit.18 mp 153–154ЊC); nmax
(KBr) 3402, 1743, 1604 cmϪ1; dH (500 MHz, CDCl3) 7.60
(1 H, d, J9.1 Hz, 8-H), 7.57 (1 H, d, J9.1 Hz, 4-H), 7.40
(1 H, d, J2.1 Hz, 1-H), 7.09 (1 H, dd, J9.1 and 2.1 Hz,
3-H), 7.06 (1 H, d, JϽ1 Hz, 5-H), 7.05 (1 H, dd,
J9.1 andϽ1 Hz, 7-H), 2.30 (3H, s, OCOCH3); dC
(125.76 MHz, CDCl3) 170.30, 154.29, 146.22, 132.79,
129.11, 128.51, 127.60, 121.24, 118.88, 118.31, 109.24,
21.07; m/z (EI) 202 (Mϩ, 12), 160 (100), 131 (26), 115
(2), 103 (10), 77 (15).
dH (500 MHz, CDCl3) 8.13 (1 H, d, J9.1 Hz, 8-H), 7.47 (1
H, d, J2.1 Hz, 5-H), 7.32 (1 H, d, J7.7 Hz, 4-H), 7.23 (1
H, dd, J7.7 and 7.7 Hz, 3-H), 7.17 (1 H, dd, J9.1 and
2.1 Hz, 7-H), 6.68 (1 H, d, J7.7 Hz, 2-H), 2.35 (3H, s,
OCOCH3); dC (125.76 MHz, CDCl3) 170.01, 151.64,
148.70, 135.15, 126.77, 125.80, 123.65, 120.02, 118.93,
118.13, 108.36, 21.14. m/z (EI) 202 (Mϩ, 12), 160 (100),
131 (40), 115 (6), 103 (29), 77 (34).
7-Acetoxy-1-hydroxynaphthalene (8c). Yield: 78%,
viscous oil; (Found: C, 71.3; H, 5.1. C12H10O3 requires C,
71.28; H, 4.98%); nmax (thin film) 3440, 1741, 1604 cmϪ1
;
2-Acetoxy-7-hydroxynaphthalene (19b). Yield: 45%,
white solid, mp 165–166ЊC (lit.19 mp 171–172ЊC); nmax
(KBr) 3400, 1740, 1602 cmϪ1; dH (500 MHz, CDCl3)
7.73 (1 H, d, J9.1 Hz, 4-H), 7.68 (1 H, d, J9.1 Hz,
5-H), 7.34 (1 H, d, J2.1 Hz, 1-H), 7.05 (1 H, d,
J2.1 Hz, 8-H), 7.03–7.00 (2 H, m, 3-H and 6-H),
2.34 (3H, s, OCOCH3); dC (125.76 MHz, CDCl3)
170.20, 154.30, 147.86, 135.25, 129.22, 128.20,
118.81, 117.80, 116.76, 115.10, 108.84, 20.91. m/z
(EI) 202 (Mϩ, 12), 160 (100), 131 (29), 115 (3), 103
(9), 77 (13).
dH (500 MHz, CDCl3) 7.68 (1 H, d, J9.1 Hz, 5-H), 7.62 (1
H, d, J7.7 Hz, 4-H), 7.27 (1 H, dd, J7.7 and 7.7 Hz,
3-H), 7.17 (1 H, d, J7.7 Hz, 2-H), 7.08 (1 H, d,
J2.1 Hz, 8-H), 6.99 (1 H, dd, J9.1 and 2.1 Hz, 6-H),
2.36 (3H, s, OCOCH3); dC (125.76 MHz, CDCl3) 170.03,
155.08, 145.34, 129.81, 129.36, 128.05, 125.84, 122.35,
118.80, 118.38, 102.82, 20.73; m/z (EI) 202 (Mϩ, 10), 160
(100), 131 (39), 115 (4), 103 (13), 77 (19).
1-Acetoxy-2-methyl-4-hydroxynaphthalene (10). Yield:
98%, brown solid, mp 122–123ЊC (from dichloromethane/
hexane) (lit.17 mp 120–122ЊC); nmax (KBr) 3412, 1734,
1601 cmϪ1
; dH (500 MHz, CDCl3) 7.96 (1 H, d,
J8.4 Hz, 5-H), 7.63 (1 H, d, J8.4 Hz, 8-H), 7.47 (1 H,
dd, J8.4 and 8.4 Hz, 7-H), 7.37 (1 H, dd, J8.4 and
8.4 Hz, 6-H), 6.34 (1 H, s, 3-H), 2.43 (3H, s, OCOCH3),
2.16 (3 H, s, CH3); dC (125.76 MHz, CDCl3) 170.34,
149.37, 137.48, 127.53, 126.93, 126.38, 124.56, 123.83,
122.09, 120.31, 110.94, 20.61, 16.26; m/z (EI) 216 (Mϩ,
10), 174 (100), 145 (12), 131 (19), 115 (25), 105 (21), 77
(18).
Acknowledgements
This work has been financially supported by the Ministero
dell’Universita e della Ricerca Scientifica (MURST PRIN,
Biocatalisi e bioconversioni) and the Italian National
Council for Research (CNR, Target Project in Biotech-
nology). We thank Dr. C. Panuccio (Cosmo S.p.A., Italy)
for IR spectra.
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